CN1384043A - Vehicular hydrogen preparing method and device - Google Patents
Vehicular hydrogen preparing method and device Download PDFInfo
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- CN1384043A CN1384043A CN02121472A CN02121472A CN1384043A CN 1384043 A CN1384043 A CN 1384043A CN 02121472 A CN02121472 A CN 02121472A CN 02121472 A CN02121472 A CN 02121472A CN 1384043 A CN1384043 A CN 1384043A
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000001257 hydrogen Substances 0.000 title claims abstract description 95
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000002360 preparation method Methods 0.000 claims abstract description 45
- 239000007788 liquid Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001868 water Inorganic materials 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims description 15
- 239000013543 active substance Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 239000000110 cooling liquid Substances 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 26
- 230000008569 process Effects 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 4
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 abstract description 2
- 239000012279 sodium borohydride Substances 0.000 abstract description 2
- 101100219382 Caenorhabditis elegans cah-2 gene Proteins 0.000 abstract 1
- 230000003139 buffering effect Effects 0.000 abstract 1
- 230000000881 depressing effect Effects 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 239000012809 cooling fluid Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
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- Fuel Cell (AREA)
Abstract
The present invention relates to the preparation of hydrogen. In the vehicular hydrogen preparing process, solid matter CaH2 a/o NaBH4, catalyst containing active matter Fe, Co, Ni, Cu or Mn and water are subjected to reaction. The hydrogen preparing apparatus includes reactors, liquid tanks, buffering tank, hydrogen purifier, depressing valve, flow rate measuring meter, pressure sensor, cooling tank with temperature sensor, etc. connected together, and the control signal from the circuit is fed to the controller. The present invented process is low in hydrogen preparation cost, high in safety and the apparatus is simple in structure, and is especially suitable for in automobile with fuel battery.
Description
Technical field
The invention belongs to technical field of hydrogen preparation, particularly relate to a kind of preparation method and device thereof that is used for the Vehicular hydrogen of fuel cell.
Background technology
Hydrogen-oxygen fuel cell is a kind of power generation assembly that directly chemical energy of oxidation of hydrogen is converted to electric energy without burning.Compare with traditional explosive motor, it is not limited by carnot's working cycle in conversion process of energy, so its energy transformation ratio will be higher than explosive motor far away.It is clean that it also has exhaust simultaneously, and noise is low, environmentally safe, and reliability and maintainability are good, and the specific energy advantages of higher makes it to become the first-selection of Move tool with electrical source of power.And fuel cell just emerged as far back as 1839, the sixties in 20th century so far 40 surplus in the period of, technical had swift and violent development again.Yet the hydrogen supply mode of the battery fuel that acts as a fuel still exists many problems at present, has seriously restricted the large-scale application of fuel cell.For promoting the practicability of fuel cell, should seek out the hydrogen supply mode of economy, facility, safety.
At present, advanced Vehicular hydrogen preparation method and device thereof are to adopt alkaline earth metal hydride, and metal borohydride hydrolysis or alkaline earth metal hydride pyrolytic method are carried out.General method is that (weight percent is 35%NaBH for the basic solution of sodium borohydride
4, 10% NaOH or KOH) by adopting TiO
2, Al
2O
3, ZrO
2Deng as carrier, Pt, Ru quicken hydrolysis reaction and generate H as the catalyzer of active substance
2But, make the application of this kind method be greatly limited, and weight percent is 35%NaBH because noble metal is rare and cost an arm and a leg
4Alkaline aqueous solution is in a metastable state and is easy to spontaneous unboiled water and separates product hydrogen, has very large potential safety hazard, also is unfavorable for prolonged preservation simultaneously.
Summary of the invention
The present invention is for solving the defective that prior art exists, and it is rare and cost an arm and a leg NaBH to overcome the existing used precious metal of method catalyzer
4The aqueous solution can be separated product hydrogen by spontaneous unboiled water, exists potential safety hazard also to be unfavorable for the problem of prolonged preservation simultaneously, and a kind of new Vehicular hydrogen preparation method and device thereof are provided.
The present invention takes solid-state reactants and solution to contact the method that hydrolysis reaction takes place and make hydrogen in reactor.Solid-state reactants is CaH
2Or be added with the NaBH of catalyzer
4Or be added with the NaBH of catalyzer
4With CaH
2Mixture, make hydrogen with the water reaction that directly is hydrolyzed; Solid-state reactants is NaBH
4Or NaBH
4With CaH
2Mixture, make hydrogen with the aqueous solution that the contains auxiliary agent reaction that is hydrolyzed.The auxiliary agent that adds solution contains Fe
2+, Fe
3+, Co
2+, Ni
2+, Cu
2+One or more; If use solid-state reactants and the mixture of catalysts then can be directly and the water reaction that is hydrolyzed, catalyzer be an active substance with one or more of Fe, Co, Ni, Cu, Mn.
The technical scheme that the preparation method of Vehicular hydrogen of the present invention adopts:
Vehicular hydrogen preparation method is taked the solid-state reactants mode that is hydrolyzed, and solid-state reactants is CaH
2Or be added with the NaBH of catalyzer
4Or be added with the NaBH of catalyzer
4With CaH
2Mixture, make hydrogen with the water reaction that directly is hydrolyzed; Solid-state reactants is NaBH
4Or NaBH
4With CaH
2Mixture, and contain Fe
2+, Fe
3+, Co
2+, Ni
2+, Cu
2+The reaction that is hydrolyzed of one or more the aqueous solution make hydrogen.The contained active substance of catalyzer that reaction adds is one or more among Fe, Co, Ni, Cu, the Mn, the amount of the contained active substance of catalyzer of adding and reactant NaBH
4The ratio of amount be 0.1%-10%.The aqueous solution that is added with auxiliary agent contains Fe
3+, Fe
2+, Co
2+, Ni
2+, Cu
2+, Mn
2+One or more, summation ion volumetric molar concentration is 0.04mol/l-0.8mol/l.
The preparation method of Vehicular hydrogen of the present invention can also take following technical measures:
Above-mentioned Vehicular hydrogen preparation method, the contained active substance of catalyzer that adds in being characterized in reacting is one or more among Fe, Co, Ni, Cu, the Mn, the amount of active substance accounts for reactant NaBH
4The proportional range of amount be 0.3%-3%; Be added with Fe in the aqueous solution of auxiliary agent
3+, Fe
2+, Co
2+, Ni
2+, Cu
2+, Mn
2+Summation ion volumetric molar concentration be 0.08mol/l-0.4mol/l.
The technical scheme that the preparation facilities of Vehicular hydrogen of the present invention adopts:
The Vehicular hydrogen preparation facilities, device, control device and refining plant composition respond, its syndeton with mode is: reactor is connected with receiver through fluid pipeline, magnetic valve, check valve, pump, reactor through gas pipeline with surge tank, hydrogen gas cleaner, reducing valve, instantaneous delivery survey meter be connected with hydrogen production device.
The preparation facilities of Vehicular hydrogen of the present invention can also be taked following technical measures:
Above-mentioned Vehicular hydrogen preparation facilities, its syndeton and mode are that reactor is an array, respectively through magnetic valve after check valve, integrated flow survey meter, pump be connected with receiver, reactor is with surge tank, hydrogen gas cleaner, reducing valve, instantaneous delivery survey meter and be connected with hydrogen production device, surge tank is equipped with pressure transmitter, and magnetic valve, flowmeter, pump, pressure transmitter all are connected with controller by circuit.
The Preparation of Hydrogen device is made up of reaction, control and refining plant three parts.Reaction unit is made of reactor, receiver and pump, check valve and magnetic valve.Control device is made of controller, integrated flow survey meter, surge tank, pressure transmitter, instantaneous delivery survey meter.Hydrogen purifies by hydrogen gas cleaner.Controller receives online surge tank hydrogen pressure signal, and the open and close of online thus signal control pump and magnetic valve, thereby Controlling System pressure is within safety range; Controller receives the integrated flow signal and controls the unlatching of different group magnetic valves, thereby reaches the purpose that the different group reactors of control are participated in reaction; Controller receives instantaneous flow rate signal, comes control pump to be operated under the different flows, thus the control hydrogen flowing quantity.The shock absorption by surge tank more simultaneously, thus realized the control of control device to reaction unit.Complete assembly adopts the method for hydrogen flowing quantity on-line Control that the flow of the solution of adding is controlled and realizes control hydrogen instantaneous delivery, thereby satisfies the fuel cell demand.
Above-mentioned Vehicular hydrogen preparation facilities, be characterized in that surge tank is 2, gas pipeline is divided into two pipelines side by side behind first surge tank, and a pipeline has magnetic valve, another pipeline has magnetic valve, surge tank, magnetic valve, and two pipelines merge the back and link to each other with hydrogen gas cleaner.When surge tank side by side started in system, its outlet magnetic valve was opened, and supplies with early stage fuel cell hydrogen, behind system stability, the outlet closed electromagnetic valve, the inlet magnetic valve is opened, when system quits work, the inlet closed electromagnetic valve, storage of hydrogen is for using next time in the surge tank.With second surge tank magnetic valve side by side be closing condition in initial reaction stage, open after the stable reaction, reaction finishes after close after a period of time.Surge tank side by side and first surge tank slow down response lag and cause system to produce the unsettled influence of hydrogen flowing quantity in the common online generation shock absorption in the stable back of reactive system.
Above-mentioned Vehicular hydrogen preparation facilities is characterized in that reactor is equipped with temperature sensor, and gas pipeline connects the instantaneous delivery survey meter behind reducing valve, and temperature sensor is connected with controller by circuit with the instantaneous delivery survey meter.For control reaction temperature between 0 ℃-100 ℃, mounting temperature sensor detects, temperature sensor passes to controller with temperature signal, by after the controller analysis to being controlled by the flow rate of the intravital circulating cooling liquid of case, reach desired reaction temperature by the Control Circulation refrigerating unit.The instantaneous delivery survey meter can detect the hydrogen instantaneous delivery, can carry out more accurate control to reaction.The temperature of reactor transmitter should be arranged at the cooling liquid outlet position.
Above-mentioned fuel cell Preparation of Hydrogen device is characterized in that control reaction temperature is between 0 ℃-100 ℃ by the cooling fluid cooling that circulates.
Above-mentioned fuel cell Preparation of Hydrogen device is characterized in that pipeline connecting mode adopts rapid-acting coupling and integrated rapid-acting coupling.
Above-mentioned fuel cell Preparation of Hydrogen device is characterized in that reactor is the integral structure of several microreactors, is made up of integrated kettle, integrated end socket, unitary flange three parts; Being to seal mutually between each minisize reaction kettle in the integrated kettle casing, is flange soft seal mode between casing and the integrated end socket; Integrated end socket is made up of microreactor end socket and gas mixed box two portions.
Reactor adopts the integrated design of a plurality of microreactors, when increasing the material reaction area, has also increased the area-volume ratio of reactor, thereby has more helped the heat radiation in the reaction process, makes reaction safety be largely increased.Integrated kettle integral body is in the casing, and logical circulating cooling liquid is controlled temperature of reaction in the gap of kettle and casing.Reaction unit is worth the measuring and calculating of adding solution amount by the integrated flow survey meter controls for which reactor participation reaction.
Above-mentioned fuel cell Preparation of Hydrogen device is characterized on the integrated kettle external box of microvave circulating cooling liquid fluid inlet and liquid outlet being arranged, and cooling fluid is arranged in the casing.Cooling fluid visual environment temperature is chosen water or oil.
Above-mentioned fuel cell Preparation of Hydrogen device is characterized between microreactor end socket and the gas mixed box unidirectional stop valve being arranged.
Above-mentioned fuel cell Preparation of Hydrogen device, be characterized in that the microreactor end socket has the charge bar that adds that inserts kettle, adding charge bar is the vesicular structure that sintering process is made, material can be selected stainless steel, copper or other high temperature materials for use, densely covered micron order aperture on the barred body, the aperture is between 3 μ m-300 μ m.The reinforced quantifying feed rod aperture spray regime of taking of liquid is reinforced.
Advantage that the present invention has and positively effect:
The preparation method of Vehicular hydrogen can guarantee to produce under the prerequisite of hydrogen rate and hydrogen flowing quantity, effectively reduce because the problem that Preparation of Catalyst cost height is difficult to be used widely to alkaline earth metal hydride or the hydrogen manufacturing of borohydride hydrolytic method, make that the method for utilization alkaline earth metal hydride or borohydride hydrolytic hydrogen production is used widely, adopt the hydrogen manufacturing of solids direct hydrolysis also to solve the major safety risks that the liquid hydrogen production process exists, also be unfavorable for the problem of prolonged preservation simultaneously.The preparation facilities of Vehicular hydrogen, have simple in structure, easy to use, the level of automation height, advantages such as the hydrogen manufacturing cost is low, installs safety, and performance is good, design science is reasonable, can be widely used in vehicle mounted hydrogen industry, is particularly useful for the preparation of hydrogen for fuel cell vehicle.
Description of drawings
Fig. 1 is a Vehicular hydrogen preparation facilities synoptic diagram of the present invention.
Fig. 2 is an integrated reactor cross-sectional view among Fig. 1.
Fig. 3 is the A-A cross-sectional view of Fig. 2.
Fig. 4 is the integrated end socket cross-sectional view of Fig. 2.
Fig. 5 is the integrated kettle cross-sectional view of Fig. 2.
Fig. 6 is a microreactor cross-sectional view of the present invention.
Embodiment
For further understanding technology contents of the present invention, characteristics and effect, exemplify following example now, and conjunction with figs. is described in detail as follows:
Embodiment 1
With reference to accompanying drawing 6, the fuel cell hydrogen preparation method, adding 50g purity is 97% NaBH in reactor
4Crystallization powder, the aperture of adopting porous sintered technology to make are that the liquid of 5 μ m adds the method adding Co that charge bar carries out quantitative aperture injection
2+Concentration is the CoCl of 0.14mol/L
2The aqueous solution sprays and uses the pressurization of 12V high-pressure pump to carry out, and flow is 0.241/h.Adopt water cooling cooling control reaction temperature in 40-60 ℃ of scope, add 0.05L solution altogether, hydrogen has been produced in reaction.
With reference to accompanying drawing 6, the fuel cell hydrogen preparation method is 97% NaBH with 25g purity
4With 25g purity be 97% CaH
2Powder is even with the catalyst mix that contains 8g active substance Co, and the carrier of catalyzer is Al
2O
3, add in the reactor.Water uses 12V high-pressure pump adding reactor to add in the charge bar, and adding the charge bar aperture is 50 μ m, carries out quantitative aperture injection flow and is controlled at 0.31/h.Temperature of reaction is controlled at 50-70 ℃, adds 0.05L solution altogether, and hydrogen has been produced in reaction.
With reference to accompanying drawing 1,2,3,4,5.The hydrogen for fuel cell vehicle preparation facilities, device, control device and refining plant composition respond, its syndeton and mode are: reactor 1 is 5 groups, be connected with receiver 5 through fluid pipeline, magnetic valve 2, check valve 3, integrated flow survey meter 7,12V high-pressure pump 6, store battery 4 starts power supply for preparation facilities.Reactor 1 and surge tank 14,, reducing valve 16, instantaneous delivery survey meter 12 be connected with hydrogen production device 13.Surge tank 10, import magnetic valve 9, outlet magnetic valve 11 together with magnetic valve 15 side by side after surge tank 14, merge the back and be connected with membrane sepn hydrogen gas cleaner 17.Surge tank 14 is equipped with pressure transmitter. Magnetic valve 2,9,11,15, integrated flow survey meter 7, instantaneous delivery instrument 12,12V high-pressure pump 6, pressure transmitter all are connected with controller 8 by circuit.Pipeline connects employing rapid-acting coupling inserting mode and connects.
The structure of reactor 1 is: reactor 1 is the integral structure of 9 microreactors, is made up of integrated kettle casing 27, integrated end socket 19, unitary flange 18 3 parts; Being to seal mutually between each minisize reaction kettle 29 in the integrated kettle casing 27, is flange soft seal mode between casing and the integrated end socket 19, and O-ring seal 24 is arranged; Integrated end socket 19 is made up of microreactor end socket and gas mixed box 21 two portions.Circulating cooling liquid fluid inlet 28 and liquid outlet 25 are arranged on the integrated kettle external box of microvave 27, in the casing 27 cooling fluid is arranged.Integrated end socket 19 has liquid adding hole quick plug 20, hydrogen outlet quick plug 22, between inner 9 microreactor end sockets and the gas mixed box 21 unidirectional stop valve 23 is arranged, and filter screen 30 is arranged in the minisize reaction kettle 29.Microreactor end socket 19 have insert kettle add charge bar 26, add the vesicular structure that charge bar 26 is made for sintering process, densely covered micron order aperture on the barred body, the aperture is at 10 μ m.The reinforced quantifying feed rod aperture spray regime of taking of liquid is reinforced.
The operation of embodiment 3: with reference to accompanying drawing 1,2,3,4,5.The hydrogen for fuel cell vehicle preparation facilities, the device that responds, control device and refining plant are formed.In 9 microreactor kettlies 29, be placed with the solid reaction powder, in the receiver 5 reaction solution be housed.When automobile fuel battery 13 needs hydrogen, controller 8 controlled opening 12V high-pressure pump 6 and magnetic valves 2, according to the need amounts of hydrogen, can open one or several electric valve 2 simultaneously, liquid is through integrated flow survey meter 7, check valve 3 and magnetic valve 2, and the solid reactant reaction that enters in reactor 1 and a group or a few bank of reactor 1 makes aequum hydrogen.Hydrogen through magnetic valve 15 with through magnetic valve 9, surge tank 10, magnetic valve 11, after reducing valve 16 decompressions, is supplied with automobile fuel battery 13 by instantaneous delivery survey meter 12 and membrane sepn hydrogen gas cleaner 17 and is used after pipeline enters surge tank 14.
When the Preparation of Hydrogen device quit work, controller 8 cut out 12V high-pressure pump 6, magnetic valve 2,9,11, closes magnetic valve 15 after for some time.Surge tank 10 side by side is when subsystem starts down, its outlet magnetic valve 11 is opened, supply with early stage fuel cell hydrogen, behind system stability, outlet magnetic valve 11 cuts out, and inlet magnetic valve 9 is opened, when system quits work, inlet magnetic valve 9 cuts out, and storage of hydrogen is for starting time use once more in the surge tank.Surge tank 10 side by side and surge tank 14 common online having an effect after reactive system is stable slow down response lag and cause system to produce the unsettled influence of hydrogen flowing quantity, and the automobile fuel battery is worked more continuously and stably.
Claims (10)
1. a Vehicular hydrogen preparation method is taked the solid-state reactants hydrolysis method, it is characterized in that: solid-state reactants is CaH
2Or be added with the NaBH of catalyzer
4Or be added with the NaBH of catalyzer
4With CaH
2Mixture, make hydrogen with the water reaction that directly is hydrolyzed; Solid-state reactants is NaBH
4Or NaBH
4With CaH
2Mixture, make hydrogen with the aqueous solution that the contains auxiliary agent reaction that is hydrolyzed; It is among Fe, Co, Ni, Cu, the Mn one or more that the catalyzer that reaction adds contains active substance, and the amount of active substance accounts for reactant NaBH
4The proportional range of amount be 0.1%-10%; The aqueous solution that is added with auxiliary agent contains Fe
3+, Fe
2+, Co
2+, Ni
2+, Cu
2+, Mn
2+One or more, summation ion volumetric molar concentration is 0.04mol/1-0.8mol/l.
2. Vehicular hydrogen preparation method according to claim 1 is characterized in that: the contained active substance of the catalyzer that adds in the reaction is one or more among Fe, Co, Ni, Cu, the Mn, and the amount of active substance accounts for reactant NaBH
4The proportional range of amount be 0.3%-3%; Be added with Fe in the aqueous solution of auxiliary agent
3+, Fe
2+, Co
2+, Ni
2+, Cu
2+, Mn
2+Summation ion volumetric molar concentration be 0.08mol/l-0.4mol/l.
3. Vehicular hydrogen preparation facilities, form by reaction unit, control device and refining plant, it is characterized in that: reactor is connected with receiver through fluid pipeline, magnetic valve, check valve, pump, reactor through gas pipeline with surge tank, hydrogen gas cleaner, reducing valve, instantaneous delivery survey meter be connected with hydrogen production device.
4. Vehicular hydrogen preparation facilities according to claim 3, it is characterized in that: reactor is an array, respectively through magnetic valve after check valve, integrated flow survey meter, pump be connected with receiver, reactor is with surge tank, hydrogen gas cleaner, reducing valve, instantaneous delivery survey meter and be connected with hydrogen production device, surge tank is equipped with pressure transmitter, and magnetic valve, flowmeter, pump, pressure transmitter all are connected with controller by circuit.
5. Vehicular hydrogen preparation facilities according to claim 4, it is characterized in that: surge tank is 2, gas pipeline is divided into two pipelines side by side behind first surge tank, article one, pipeline has magnetic valve, another pipeline has magnetic valve, surge tank, magnetic valve, and two pipelines merge the back and link to each other with hydrogen gas cleaner.
6. Vehicular hydrogen preparation facilities according to claim 4, it is characterized in that: reactor is equipped with temperature sensor, and temperature sensor is connected with controller by circuit.
7. Vehicular hydrogen preparation facilities according to claim 3 is characterized in that: pipeline connecting mode adopts rapid-acting coupling and integrated rapid-acting coupling.
8. according to the described Vehicular hydrogen preparation facilities of claim 3-7, it is characterized in that: reactor is made up of integrated kettle, integrated end socket, unitary flange three parts for the integral structure of several microreactors; Being to seal mutually between each minisize reaction kettle in the integrated kettle casing, is flange soft seal mode between casing and the integrated end socket; Integrated end socket is made up of microreactor end socket and gas mixed box two portions.
9. Vehicular hydrogen preparation facilities according to claim 8 is characterized in that: on the integrated kettle external box of microvave circulating cooling liquid fluid inlet and liquid outlet are arranged.
10. Vehicular hydrogen preparation facilities according to claim 8 is characterized in that: between microreactor end socket and the gas mixed box unidirectional stop valve is arranged, between microreactor end socket and microreactor kettle filtering net is arranged; The microreactor end socket has the charge bar that adds that inserts kettle, and adding charge bar is vesicular structure, the micron order aperture that gathers on the barred body, and the aperture is between 3 μ m-300 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021214727A CN1158212C (en) | 2002-06-25 | 2002-06-25 | Vehicular hydrogen preparing method and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021214727A CN1158212C (en) | 2002-06-25 | 2002-06-25 | Vehicular hydrogen preparing method and device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1384043A true CN1384043A (en) | 2002-12-11 |
| CN1158212C CN1158212C (en) | 2004-07-21 |
Family
ID=4744985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021214727A Expired - Fee Related CN1158212C (en) | 2002-06-25 | 2002-06-25 | Vehicular hydrogen preparing method and device |
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|---|---|
| CN (1) | CN1158212C (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100361337C (en) * | 2004-10-22 | 2008-01-09 | 上海神力科技有限公司 | A fuel cell that responds quickly to sudden increases in output power |
| CN101390238B (en) * | 2006-11-28 | 2011-09-07 | 燃料电池能量公司 | Fuel cell system including reliable gas supply lines |
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| CN103979488A (en) * | 2013-02-07 | 2014-08-13 | 北京华泰天成科技发展有限公司 | Technology using magnesium metal for continuous hydrogen and magnesium hydroxide production |
| CN103979489A (en) * | 2013-02-07 | 2014-08-13 | 北京华泰天成科技发展有限公司 | Combined heat and power technology using magnesium metal or aluminum for continuous hydrogen production |
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| CN109950588A (en) * | 2019-04-08 | 2019-06-28 | 镁格氢动能源技术(苏州)有限公司 | A kind of electric generating station system based on solid hydrogen technology |
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| CN111439724A (en) * | 2020-05-12 | 2020-07-24 | 河南中氢动力研究院有限公司 | Hydrogen production system, apparatus and method |
| US11141692B2 (en) | 2012-08-30 | 2021-10-12 | Element 1 Corp | Hydrogen generation assemblies and hydrogen purification devices |
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2002
- 2002-06-25 CN CNB021214727A patent/CN1158212C/en not_active Expired - Fee Related
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| CN100361337C (en) * | 2004-10-22 | 2008-01-09 | 上海神力科技有限公司 | A fuel cell that responds quickly to sudden increases in output power |
| CN101390238B (en) * | 2006-11-28 | 2011-09-07 | 燃料电池能量公司 | Fuel cell system including reliable gas supply lines |
| TWI392644B (en) * | 2008-12-10 | 2013-04-11 | Univ Nat Central | The method of sodium borohydride reacting with water to produce hydrogen |
| US11738305B2 (en) | 2012-08-30 | 2023-08-29 | Element 1 Corp | Hydrogen purification devices |
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| CN107697885A (en) * | 2012-08-30 | 2018-02-16 | 埃利门特第公司 | Device for producing hydrogen |
| CN103979488A (en) * | 2013-02-07 | 2014-08-13 | 北京华泰天成科技发展有限公司 | Technology using magnesium metal for continuous hydrogen and magnesium hydroxide production |
| CN103979489A (en) * | 2013-02-07 | 2014-08-13 | 北京华泰天成科技发展有限公司 | Combined heat and power technology using magnesium metal or aluminum for continuous hydrogen production |
| CN103979488B (en) * | 2013-02-07 | 2016-04-06 | 北京华泰天成科技发展有限公司 | Adopt the technique of MAGNESIUM METAL continuous seepage hydrogen and magnesium hydroxide |
| CN103979489B (en) * | 2013-02-07 | 2016-04-06 | 北京华泰天成科技发展有限公司 | Adopt the cogeneration technology of MAGNESIUM METAL or aluminium continuous hydrogen production |
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| CN107799792B (en) * | 2016-09-05 | 2023-08-01 | 天津新氢动力科技有限公司 | Throwing type solid sodium borohydride fuel cell hydrogen supply system and method |
| CN107959035A (en) * | 2016-10-17 | 2018-04-24 | 深圳市雄韬电源科技股份有限公司 | The emission recycling circulation hydrogen generating system of hydrogen fuel cell |
| CN109415205A (en) * | 2017-04-22 | 2019-03-01 | 银河测试有限公司 | Equipment for generating hydrogen |
| CN107570099B (en) * | 2017-09-28 | 2023-08-25 | 上海国强生化工程装备有限公司 | Tank pressure control device of parallel reactor |
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| CN109950588A (en) * | 2019-04-08 | 2019-06-28 | 镁格氢动能源技术(苏州)有限公司 | A kind of electric generating station system based on solid hydrogen technology |
| CN110171805A (en) * | 2019-06-26 | 2019-08-27 | 中国计量大学 | A kind of detection method of hydrogen purification apparatus and its purifying hydrogen efficiency |
| CN111439724A (en) * | 2020-05-12 | 2020-07-24 | 河南中氢动力研究院有限公司 | Hydrogen production system, apparatus and method |
| CN111439724B (en) * | 2020-05-12 | 2023-12-19 | 河南中氢动力研究院有限公司 | Hydrogen production system, device and hydrogen production method |
| US12187612B2 (en) | 2021-06-15 | 2025-01-07 | Element 1 Corp | Hydrogen generation assemblies |
| US20230182100A1 (en) * | 2021-12-13 | 2023-06-15 | Hyundai Motor Company | Dehydrogenation reaction apparatus and control method thereof |
| CN119812406A (en) * | 2024-11-30 | 2025-04-11 | 北京氢源智能科技有限公司 | A hydrogen-powered drone |
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